CN101864045A - Preparation method of chemically crosslinked nanocomposite hydrogel - Google Patents
Preparation method of chemically crosslinked nanocomposite hydrogel Download PDFInfo
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- CN101864045A CN101864045A CN 201010159507 CN201010159507A CN101864045A CN 101864045 A CN101864045 A CN 101864045A CN 201010159507 CN201010159507 CN 201010159507 CN 201010159507 A CN201010159507 A CN 201010159507A CN 101864045 A CN101864045 A CN 101864045A
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Abstract
The invention relates to a preparation method of a chemically crosslinked nanocomposite hydrogel, which comprises the following steps: (1) adding water, hydrophobic monomers and a surfactant into a container, raising the temperature to a certain temperature, adding a water-soluble initiator, carrying out reaction for 1h-2h, adding acetone solution of a polymerizable photoinitiator into a system, completing the adding within 6h, stopping heating, obtaining nano-microspheres with photo-initiation activity and carrying out dialysis on the prepared microspheres in distillated water for 72h; and (2) adding emulsion of the microspheres with the photo-initiation activity in the concentration of 5%-40% after the dialysis of the step (1) into water-soluble monomers for light radiation. The preparation method has the advantages of simpleness, wide sources of raw materials, high polymerization efficiency and fast polymerization speed, and is applicable to industrial production; and the obtained nanocomposite hydrogel has excellent mechanical properties and good stability.
Description
Technical field
The invention belongs to the preparation field of Nanometer composite hydrogel, particularly relate to a kind of preparation method of chemically crosslinked nanocomposite hydrogel.
Background technology
Macromolecule hydrogel is a kind of special soft wet materials, be to have the crosslinking hydrophilic polymer of three-dimensional net structure and the system of solvent composition, it can be in water swelling but do not dissolve, and can keep certain shape.The binding effect of macromolecule hydrogel is varied, and chemical covalent linkage effect is arranged, and physics weak key action (as hydrogen bond, electrostatic interaction, Van der Waals force etc.) is also arranged, and also can form crosslinking structure by modes such as the mutual IPN of segment, entanglement.
The synthetic hydrogel material aspect physical properties than other any synthetic material more as biological tissue, thereby be expected to be widely used in fields such as bio-medicals.Yet tradition utilizes the chemically crosslinked water-setting of chemical cross-linking agent preparation because the cross-linking density inequality, has caused the stress concentration when stressed easily, makes its poor mechanical property, has seriously limited its application in every respect.
In order to improve the mechanical property of gel, Haraguchi etc. have reported Nanometer composite hydrogel, are linking agent with the hectorite, are crosslinked action with the interaction between polymkeric substance and clay, and in-situ polymerization has generated clay/polymkeric substance composite aquogel.It forms the uneven network of cross-linking density when having avoided the chemical cross-linking agent reaction, thereby has greatly improved the mechanical property of gel.In addition, a series of novel Nano microsphere composite aquogels also are in the news, and these gels all have excellent mechanical property and swelling behavior.Yet all these Nanometer composite hydrogels all are based on the effect of physics binding and form, and are easily destroyed at comparatively high temps (as 80 ℃) or strong acid-base condition lower network structure, thereby the mechanical property of gel and swelling behavior are all disappeared.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of chemically crosslinked nanocomposite hydrogel, and this method is simple, and raw material sources are extensive, the polymerization efficiency height, and polymerization velocity is fast, is suitable for suitability for industrialized production; The Nanometer composite hydrogel of gained has excellent mechanical property and satisfactory stability.
The preparation method of a kind of chemically crosslinked nanocomposite hydrogel of the present invention comprises:
(1) whipping appts, reflux and N are equipped with in water, hydrophobic monomer, tensio-active agent adding
2In the container of inlet, be heated to 75 ℃-85 ℃, add water soluble starter, reaction 1h-2h adds the acetone soln 4-6ml of polymerizable light trigger, and added in 6 hours in system, promptly get and have light-initiated active Nano microsphere, the microballoon that makes was dialysed in distilled water 72 hours; Described hydrophobic monomer accounts for the 5%-40% of system total mass, the 0.1%-3% of surfactant comprise hydrophobic monomer quality, and water soluble starter accounts for the 0.1%-0.3% of hydrophobic monomer quality, and the polymerizable light trigger accounts for the 2%-10% of hydrophobic monomer quality; The system total mass is the summation of water, hydrophobic monomer, tensio-active agent, water soluble starter and polymerizable light trigger;
(2) with light-initiated active microballoon emulsion and water-soluble monomer after step (1) dialysis, be 1 according to mass ratio: (0.3-1) mix obtaining pre-polymerization liquid, pre-polymerization liquid illumination 5-10min promptly gets Nanometer composite hydrogel.
Hydrophobic monomer in the described step (1) is monomers such as vinylbenzene, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate.
Tensio-active agent in the described step (1) is a sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, dioctyl sodium sulfosuccinate, Sodium glycocholate, sodium stearate, palmityl trimethyl ammonium chloride, a kind of in the dodecyl dimethyl ethyl brometo de amonio.
Water soluble starter in the described step (1) is Potassium Persulphate, ammonium persulphate or sodium sulfate.
Polymerizable light trigger in the described step (1) is the photoinitiator that end group has vinyl groups, as 2-hydroxyl dimethyl benzene acetone methacrylic acid ethylene glycol, 4-acryloxy benzophenone, 2-hydroxyl-4-acryloyl-oxy oxethyl-diphenyl-ketone, 2-hydroxy-4-methyl acryloxy benzophenone, 4-propenyloxy group-2-dihydroxy benaophenonel.
Light-initiated active nano microballoon yield＞98% in the described step (1), particle diameter is 50-150nm, emulsion solid content is between 5%-40%.
Water-soluble monomer in the described step (2) is one or more in N-isopropylacrylamide, acrylamide, vinylformic acid, methacrylic acid-2-hydroxy methacrylate, the vinyl pyrrolidone etc.
Nanometer composite hydrogel breaking tenacity in the described step (2) is 10KPa-600KPa, and maximum extension at break reaches 2500%.
Nanometer composite hydrogel in the described step (2) has good stability, still has the regular network structure of gel and keep good swelling behavior under high temperature, strong acid-base condition.
Utilization of the present invention has light-initiated active Nano microsphere and is cross-linking set, trigger monomer is at the in-situ polymerization of microsphere surface under illumination condition, realize microballoon and the chemically crosslinked of molecule interchain, and then construct network structure that preparation is based on the Nanometer composite hydrogel of chemically crosslinked effect.The preparation of this Nanometer composite hydrogel is characterized in that at first realizing the chamical binding of light trigger on the Nano microsphere surface, then water-soluble monomer and less water is added in the microballoon emulsion, reacts under illumination condition.
Beneficial effect
(1) preparation method of the present invention is simple, and raw material sources are extensive, the polymerization efficiency height, and polymerization velocity is fast, is suitable for suitability for industrialized production;
(2) Nanometer composite hydrogel of gained of the present invention has excellent mechanical property, and maximum breaking tenacity surpasses 600KPa, and maximum extension at break reaches 2500%; Have satisfactory stability, under comparatively high temps, strong acid, highly basic effect, still keep good network structure and performance.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With the 34g deionized water, 24g vinylbenzene, whipping appts, reflux and N are equipped with in the adding of 0.72g sodium lauryl sulphate
2In the there-necked flask of inlet, stir logical N
2, drip 2ml 3.6% persulfate aqueous solution after being warming up to 75 ℃, react after 1 hour, adding is dissolved with the acetone soln 6ml of 0.48g polymerizable light trigger 2-hydroxyl dimethyl benzene acetone methacrylic acid ethylene glycol in the system, adds in 6 hours.Stop logical N afterwards
2, stopping heating, reaction stops, and the microballoon that makes was dialysed in distilled water 72 hours.Get response type emulsion 20g, add the 6g acrylamide monomer in the stirring, illumination 5 minutes promptly makes chemically crosslinked nanocomposite hydrogel.
Embodiment 2
With the 55g deionized water, the 3g methyl acrylate, whipping appts, reflux and N are equipped with in the adding of 0.003g Sodium dodecylbenzene sulfonate
2In the there-necked flask of inlet, stir logical N
2, drip 2ml 0.15% sodium persulfate aqueous solution after being warming up to 80 ℃, react after 1 hour, adding is dissolved with the acetone soln 4ml of 0.3g polymerizable light trigger 2-hydroxyl dimethyl benzene acetone methacrylic acid ethylene glycol in the system, adds in 6 hours.Stop logical N afterwards
2, stopping heating, reaction stops, and the microballoon that makes was dialysed in distilled water 72 hours.Get response type emulsion 20g, add the 20g Acrylic Acid Monomer in the stirring, illumination 5 minutes promptly makes chemically crosslinked nanocomposite hydrogel.
Embodiment 3
With the 45g deionized water, the 12g ethyl propenoate, whipping appts, reflux and N are equipped with in the adding of 0.36g palmityl trimethyl ammonium chloride
2In the there-necked flask of inlet, stir logical N
2, drip 3ml 0.8% persulfate aqueous solution after being warming up to 85 ℃, react after 1 hour, adding is dissolved with the acetone soln 5ml of 0.24g response type light trigger 2-hydroxyl dimethyl benzene acetone methacrylic acid ethylene glycol in the system, adds in 6 hours.Stop logical N afterwards
2, stopping heating, reaction stops, and the microballoon that makes was dialysed in distilled water 72 hours.Get response type emulsion 20g, add 6g N-isopropylacrylamide monomer in the stirring, illumination 5 minutes promptly makes chemically crosslinked nanocomposite hydrogel.
Embodiment 4
With the 38g deionized water, the 18g butyl acrylate, whipping appts, reflux and N are equipped with in the adding of 0.18g sodium stearate
2In the there-necked flask of inlet, stir logical N
2, drip 4ml 1.35% ammonium persulfate aqueous solution after being warming up to 75 ℃, react after 1 hour, adding is dissolved with the acetone soln 5ml of 1.8g response type light trigger 2-hydroxyl dimethyl benzene acetone methacrylic acid ethylene glycol in the system, adds in 6 hours.Stop logical N afterwards
2, stopping heating, reaction stops, and the microballoon that makes was dialysed in distilled water 72 hours.Get response type emulsion 20g, add the 15g Acrylic Acid Monomer in the stirring, illumination 5 minutes promptly makes chemically crosslinked nanocomposite hydrogel.
Embodiment 5
With the 50g deionized water, the 6g methyl methacrylate, whipping appts, reflux and N are equipped with in the adding of 0.12g Sodium glycocholate
2In the there-necked flask of inlet, stir logical N
2, drip 4ml 0.45% ammonium persulfate aqueous solution after being warming up to 75 ℃, react after 1 hour, adding is dissolved with the acetone soln 6ml of 0.3g response type light trigger 2-hydroxyl dimethyl benzene acetone methacrylic acid ethylene glycol in the system, adds in 6 hours.Stop logical N afterwards
2, stopping heating, reaction stops, and the microballoon that makes was dialysed in distilled water 72 hours.Get response type emulsion 20g, add 10g methacrylic acid-2-hydroxy methacrylate monomer in the stirring, illumination 5 minutes promptly makes chemically crosslinked nanocomposite hydrogel.
Embodiment 6
With the 46g deionized water, 12g vinylbenzene, whipping appts, reflux and N are equipped with in the adding of 0.12g tensio-active agent dioctyl sodium sulfosuccinate
2In the there-necked flask of inlet, stir logical N
2, drip 2ml 0.6% sodium persulfate aqueous solution after being warming up to 80 ℃, react after 1 hour, adding is dissolved with the acetone soln 6ml of 0.24g response type light trigger 2-hydroxyl dimethyl benzene acetone methacrylic acid ethylene glycol in the system, adds in 6 hours.Stop logical N afterwards
2, stopping heating, reaction stops, and the microballoon that makes was dialysed in distilled water 72 hours.Get response type emulsion 20g, add the 12g vinyl pyrrolidone in the stirring, illumination 5 minutes promptly makes chemically crosslinked nanocomposite hydrogel.
Claims (8)
1. the preparation method of a chemically crosslinked nanocomposite hydrogel comprises:
(1) whipping appts, reflux and N are equipped with in water, hydrophobic monomer, tensio-active agent adding
2In the container of inlet, be heated to 75 ℃-85 ℃, add water soluble starter, reaction 1h-2h adds the acetone soln 4-6ml of polymerizable light trigger, and added in 6 hours in system, promptly get and have light-initiated active Nano microsphere, the microballoon that makes was dialysed in distilled water 72 hours; Described hydrophobic monomer accounts for the 5%-40% of system total mass, the 0.1%-3% of surfactant comprise hydrophobic monomer quality, and water soluble starter accounts for the 0.1%-0.3% of hydrophobic monomer quality, and the polymerizable light trigger accounts for the 2%-10% of hydrophobic monomer quality; The system total mass is the summation of water, hydrophobic monomer, tensio-active agent, water soluble starter and polymerizable light trigger;
(2) with light-initiated active microballoon emulsion and water-soluble monomer after step (1) dialysis, be 1 according to mass ratio: (0.3-1) mix obtaining pre-polymerization liquid, pre-polymerization liquid illumination 5-10min promptly gets Nanometer composite hydrogel.
2. the preparation method of a kind of chemically crosslinked nanocomposite hydrogel according to claim 1, it is characterized in that: the hydrophobic monomer in the described step (1) is vinylbenzene, methyl acrylate, ethyl propenoate, butyl acrylate or methyl methacrylate.
3. the preparation method of a kind of chemically crosslinked nanocomposite hydrogel according to claim 1, it is characterized in that: the tensio-active agent in the described step (1) is sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, dioctyl sodium sulfosuccinate, Sodium glycocholate, sodium stearate, palmityl trimethyl ammonium chloride or dodecyl dimethyl ethyl brometo de amonio.
4. the preparation method of a kind of chemically crosslinked nanocomposite hydrogel according to claim 1, it is characterized in that: the water soluble starter in the described step (1) is Potassium Persulphate, ammonium persulphate or sodium sulfate.
5. the preparation method of a kind of chemically crosslinked nanocomposite hydrogel according to claim 1, it is characterized in that: the polymerizable light trigger in the described step (1) is the photoinitiator that end group has vinyl groups: 2-hydroxyl dimethyl benzene acetone methacrylic acid ethylene glycol, 4-acryloxy benzophenone, 2-hydroxyl-4-acryloyl-oxy oxethyl-diphenyl-ketone, 2-hydroxy-4-methyl acryloxy benzophenone or 4-propenyloxy group-2-dihydroxy benaophenonel.
6. the preparation method of a kind of chemically crosslinked nanocomposite hydrogel according to claim 1 is characterized in that: light-initiated active nano microballoon yield＞98% in the described step (1), and particle diameter is 50-150nm, emulsion solid content is between 5%-40%.
7. the preparation method of a kind of chemically crosslinked nanocomposite hydrogel according to claim 1, it is characterized in that: the water-soluble monomer in the described step (2) is one or more in N-isopropylacrylamide, acrylamide, vinylformic acid, methacrylic acid-2-hydroxy methacrylate, the vinyl pyrrolidone.
8. the preparation method of a kind of chemically crosslinked nanocomposite hydrogel according to claim 1, it is characterized in that: the Nanometer composite hydrogel breaking tenacity in the described step (2) is 10KPa-600KPa, and maximum extension at break reaches 2500%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103194800A (en) * | 2013-02-28 | 2013-07-10 | 吉林大学 | Preparation method of polymer photonic crystal with photonic band gap capable of being adjusted in wide range |
| CN106496394A (en) * | 2016-11-01 | 2017-03-15 | 长春工业大学 | A kind of cation emulsion particle toughening hydrophobic association hydrogel and preparation method |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
| CN108283938A (en) * | 2018-01-25 | 2018-07-17 | 丹东明珠特种树脂有限公司 | Strong acid type cationic resin catalyst and its overlapping application of light petrol C 5/C 6 olefin |
| CN108794671A (en) * | 2018-04-10 | 2018-11-13 | 南京捷纳思新材料有限公司 | A kind of preparation method of polystyrene emulsion |
| CN110041464A (en) * | 2019-04-04 | 2019-07-23 | 中山大学 | A kind of high intensity photon crystal water gel and its preparation method and application |
| CN110845669A (en) * | 2019-11-28 | 2020-02-28 | 中国科学院新疆理化技术研究所 | Composite hydrogel for explosive detection and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000034804A1 (en) * | 1998-12-11 | 2000-06-15 | Bausch & Lomb Surgical, Inc. | High refractive index hydrogel compositions for ophthalmic implants |
| JP2001240627A (en) * | 1999-12-20 | 2001-09-04 | Jsr Corp | Cationic hollow cross-linked polymer particle and production method therefor |
| CN1746199A (en) * | 2005-09-30 | 2006-03-15 | 清华大学 | Direct synthesis of temperate sensitive aquogel by ultraviolet radiant polymerization |
| CN1858074A (en) * | 2006-04-17 | 2006-11-08 | 江南大学 | Process for preparing surface functional crosslinking polystyrene micro ball |
| CN101531742A (en) * | 2009-04-14 | 2009-09-16 | 东华大学 | Method for preparing nanometer composite aquagel using nanometer microsphere as junction |
-
2010
- 2010-04-27 CN CN2010101595073A patent/CN101864045B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000034804A1 (en) * | 1998-12-11 | 2000-06-15 | Bausch & Lomb Surgical, Inc. | High refractive index hydrogel compositions for ophthalmic implants |
| JP2001240627A (en) * | 1999-12-20 | 2001-09-04 | Jsr Corp | Cationic hollow cross-linked polymer particle and production method therefor |
| CN1746199A (en) * | 2005-09-30 | 2006-03-15 | 清华大学 | Direct synthesis of temperate sensitive aquogel by ultraviolet radiant polymerization |
| CN1858074A (en) * | 2006-04-17 | 2006-11-08 | 江南大学 | Process for preparing surface functional crosslinking polystyrene micro ball |
| CN101531742A (en) * | 2009-04-14 | 2009-09-16 | 东华大学 | Method for preparing nanometer composite aquagel using nanometer microsphere as junction |
Non-Patent Citations (1)
| Title |
|---|
| 《Biotechnol. Prog.》 20051206 Ram Mohan Kripa Ramanan et al Development of a Temperature-Sensitive Composite Hydrogel for Drug Delivery Applications 118-125 1-8 第22卷, 第1期 2 * |
Cited By (10)
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| CN103194800A (en) * | 2013-02-28 | 2013-07-10 | 吉林大学 | Preparation method of polymer photonic crystal with photonic band gap capable of being adjusted in wide range |
| CN103194800B (en) * | 2013-02-28 | 2016-06-01 | 吉林大学 | The preparation method of forbidden photon band adjustable polymer photon crystal on a large scale |
| CN106496394A (en) * | 2016-11-01 | 2017-03-15 | 长春工业大学 | A kind of cation emulsion particle toughening hydrophobic association hydrogel and preparation method |
| CN107936167A (en) * | 2017-12-21 | 2018-04-20 | 苏州希尔盖森新材料有限公司 | One kind has hydrophilic polystyrene microsphere |
| CN108283938A (en) * | 2018-01-25 | 2018-07-17 | 丹东明珠特种树脂有限公司 | Strong acid type cationic resin catalyst and its overlapping application of light petrol C 5/C 6 olefin |
| CN108794671A (en) * | 2018-04-10 | 2018-11-13 | 南京捷纳思新材料有限公司 | A kind of preparation method of polystyrene emulsion |
| CN108794671B (en) * | 2018-04-10 | 2020-10-09 | 南京捷纳思新材料有限公司 | Preparation method of polystyrene emulsion |
| CN110041464A (en) * | 2019-04-04 | 2019-07-23 | 中山大学 | A kind of high intensity photon crystal water gel and its preparation method and application |
| CN110041464B (en) * | 2019-04-04 | 2021-09-03 | 中山大学 | High-strength photonic crystal hydrogel and preparation method and application thereof |
| CN110845669A (en) * | 2019-11-28 | 2020-02-28 | 中国科学院新疆理化技术研究所 | Composite hydrogel for explosive detection and preparation method thereof |
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